Corrosion Science 53 (2011) 263–275

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Inhibitive properties, thermodynamic and quantum chemical studies of alloxazine

on mild steel corrosion in H2SO4
N.O. Obi-Egbedi a, I.B. Obot b,⇑
a
Department of Chemistry, University of Ibadan, Ibadan, Nigeria
b
Department of Chemistry, Faculty of Science, University of Uyo, P.M.B. 1017, Uyo, Akwa Ibom State, Nigeria

a r t i c l e i n f o a b s t r a c t

Article history: Alloxazine (ALLOX) was tested as corrosion inhibitor for mild steel in 0.5 M H2SO4 solution using non-
Received 30 April 2010 electrochemical technique (gravimetric and UV–Visible spectrophotometric measurements) at 303–
Accepted 9 September 2010 333 K. ALLOX acts as inhibitor for mild steel in acidic medium. Inhibition efficiency increases with
Available online 17 September 2010
increase in concentration of ALLOX but decrease with rise in temperature. The adsorption of ALLOX
was found to follow Temkin adsorption isotherm model. Both the activation and thermodynamic param-
Keywords: eters governing the adsorption process were calculated and discussed. The adsorption follows a first-
A. Alloxazine
order kinetics. DFT study gave further insight into the mechanism of inhibition action of ALLOX.
B. Mild steel
C. Sulphuric acid
Ó 2010 Elsevier Ltd. All rights reserved.
D. Density functional theory (DFT)

1. Introduction Lumichrome (7,8-dimethylalloxazine), for example was found to

Corrosion inhibitors have been widely used in stimulation oper-
ations in petroleum wells [1,2]. In these operations acid solutions
at temperatures up to 333 K are often employed to remove iron
oxides and carbonated minerals [3]. In such aggressive medium,
the use of corrosion inhibitors is one of the most common, effective
and economic methods to protect metals in acid media [4].
The majority of the well-known inhibitors are organic com-
pounds containing heteroatoms such as oxygen, nitrogen or sul-
phur, and multiple bonds, which allow an adsorption on the
metal surface [5–7]. It has been observed that the adsorption of
these inhibitors depends on the physico-chemical properties of
the functional groups and the electron density at the donor atom.
The adsorption occurs due to the interaction of the lone pair and/
or p-orbitals of inhibitor with d-orbitals of the metal surface
atoms, which evokes a greater adsorption of the inhibitor mole-
cules onto the surface, leading to the formation of a corrosion pro-
tection film [8–10]. Furthermore, adsorption is also influenced by
the structure and the charge of metal surface, and the type of test-
ing electrolyte [11]. The choice of effective inhibitors is based on
their mechanism of action and electron-donating ability. The sig-
nificant criteria involved in this selection are molecular structure,
electron density on the donor atoms, solubility and dispersibility
[12–15].
Recently, interest in alloxazines has intensified because of their
important role in a wide range of biological systems [16].
⇑ Corresponding author. Tel.: +234 8067476065.
E-mail address: proffoime@yahoo.com (I.B. Obot).
inhibit flavin reductase in living Escherichia coli cells [17]. Another
interesting application is in an optical transistor device with a thin
film of Lumichrome on conductive SnO2 glass [18]. A further point
of interest is the possibility of using alloxazines to sensitize the
photooxidation of substituted phenols in water [19]. However,
there is no literature to date about the corrosion inhibitive effect
of alloxazine on mild steel in H2SO4 solution.
The aim of this paper therefore is to explore the use of alloxazine
as an acid corrosion inhibitor for mild steel surface in sulphuric acid
solution using gravimetric method. The effect of temperature on
corrosion and inhibition processes are thoroughly assessed and dis-
cussed. Kinetic and thermodynamic parameters were calculated and
discussed in detail. UV–Visible spectroscopy together with quantum
chemical study using density functional theory were further em-
ployed to provide additional insight into the mechanism of inhibi-
tory action.
2. Experimental method
2.1. Material
Test were performed on a freshly prepared sheet of mild steel of
the following composition (wt.%): 0.13% C, 0.18% Si, 0.39% Mn,
0.40% P, 0.04% S, 0.025% Cu, and bal. Fe. Specimens used in the
weight loss experiment were mechanically cut into 5.0 cm 
4.0 cm  0.8 cm dimensions, then abraded with SiC abrasive
papers 320, 400 and 600 grit, respectively, washed in absolute eth-
anol and acetone, dried in room temperature and stored in a mois-
ture free desiccator before their use in corrosion studies [5,6].

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.09.020
264 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

ALLOX. It is evident that ALLOX is a heterocyclic compound con-

taining nitrogen and oxygen atoms, which could easily be proton-
ated in acidic solution, and several p-electrons exist in this
molecule.

2.3. Solutions

The aggressive solutions, 0.5 M H2SO4 were prepared by dilu-

Fig. 1. Molecular structure of alloxazine (ALLOX).
2.2. Inhibitor
Alloxazine (ALLOX) was purchased from SIGMA–ALDRICH and
used as inhibitor. Stock solution was made in 10:1 water:methanol
mixture to ensure solubility [20]. This stock solution was used for
all experimental purposes. Fig. 1 shows the molecular structure of
tion of analytical grade 98% H2SO4 with distilled water. The con-
centration range of ALLOX was 2–10 lM.
2.4. Gravimetric measurements
The gravimetric method (weight loss) is probably the most
widely used method of inhibition assessment [21–24]. The sim-
plicity and reliability of the measurement offered by the weight

Fig. 2. Variation of weight loss against time for mild steel corrosion in 0.5 M H2SO4 in the presence of different concentrations of ALLOX at (a) 303 (b) 313 (c) 323 and (d)
333 K.
 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275 265

Fig. 2 (continued)

loss method is such that the technique forms the baseline method DW
q¼ ð1Þ
of measurement in many corrosion monitoring programmes [25]. St
Weight loss measurements were conducted under total immer-
where W is the average weight loss of three mild steel sheets, S the
sion using 250 mL capacity beakers containing 200 mL test solu-
total area of one mild steel specimen, and t is the immersion time
tion at 303–333 K maintained in a thermostated water bath.
(10 h). With the calculated corrosion rate, the inhibition efficiency
The mild steel coupons were weighed and suspended in the bea-
(%I) was calculated as follows [28,29]:
ker with the help of rod and hook. The coupons were retrieved at
 
2 h interval progressively for 10 h, washed thoroughly in 20% q1  q2
%I ¼  100 ð2Þ
NaOH solution containing 200 g/l of zinc dust [10] with bristle q1
brush, rinsed severally in deionized water, cleaned, dried in ace-
tone, and re-weighed. The weight loss, in grammes, was taken where q1 and q2 are the corrosion rates of the mild steel coupons in
as the difference in the weight of the mild steel coupons before the absence and presence of inhibitor, respectively.
and after immersion in different test solutions. Then the tests
were repeated at different temperatures. In order to get good 2.5. Spectrophotometric measurements
reproducibility, experiments were carried out in triplicate. In this
present study, the standard deviation values among parallel trip- UV–Visible absorption spectrophotometric method was carried
licate experiments were found to be smaller than 5%, indicating out on the prepared mild steel samples after immersion in 0.5 M
good reproducibility. H2SO4 with and without addition of 10 lM of alloxazine at 303 K
The corrosion rate (q) in mg cm2 h1 was calculated from the for 3 days. All the spectra measurements were carried out using
following equation [26,27]: a Perkin-Elmer UV–Visible Lambda 2 spectrophotometer.
266 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

θ
Fig. 5. Variation of the degree of surface coverage (h) with the logarithm of bulk
concentration of ALLOX.

Fig. 3. The relationship between corrosion rate and temperature in the absence and
presence of different concentrations of ALLOX.
2.6. Computational details
B3LYP, a version of the DFT method that uses Becke’s three
parameter functional (B3) and includes a mixture of HF with DFT
exchange terms associated with the gradient corrected correlation
functional of Lee, Yang and Parr (LYP) [30], was used in this paper
to carry out quantum calculations. Then, full geometry optimiza-
tion together with the vibrational analysis of the optimized struc-
tures of the inhibitor was carried out at the highest (B3LYP/6-31G
(d,p) level of theory using Spartan’06 V112 program package [31]
in order to determine whether they correspond to a maximum or
a minimum in the potential energy curve. The theoretical parame-
ters were calculated for molecules in gas phase, aqueous phase and
in protonated form for comparison. It is well known that the phe-
nomenon of electrochemical corrosion occurs in liquid phase. As a
result, it was necessary to include the effect of a solvent in the
computational calculations. In the Spartan’06 V112 program, SCRF
methods (Self-consistent reaction field) were used to perform cal-
culations in solution. These methods model the solvent as a contin-
uum of uniform dielectric constant and the solute is placed in the
cavity within it.

Table 1
Calculated values of corrosion rate and inhibition efficiency for mild steel corrosion for mild steel in 0.5 M H2SO4 in the absence and presence of ALLOX at 303–333 K.

System/concentration Corrosion rate (mg cm2 h1) Inhibition efficiency (%I)

303 K 313 K 323 K 333 K 303 K 313 K 323 K 333 K
Blank 0.99 1.84 2.84 4.40 – – – –
2 lM 0.89 1.68 2.67 4.14 10 09 07 06
4 lM 0.50 1.08 1.07 3.56 49 41 35 20
6 lM 0.24 0.55 1.19 3.42 76 70 59 22
8 lM 0.11 0.33 1.01 2.62 89 82 65 40
10 lM 0.03 0.23 0.70 2.22 96 88 76 50

Fig. 4. Variation of inhibition efficiency of ALLOX with temperature.

 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275
3. Results and discussion
3.1. Effect of alloxazine on weight loss, corrosion rate and inhibition
efficiency
Corrosion inhibition performance of organic compounds as cor-
rosion inhibitors can be evaluated using electrochemical and
chemical techniques. For the chemical methods, a weight loss mea-
surement is ideally suited for long term immersion test. Corrobora-
tive results between weight loss and other techniques have been
reported [32–35].
The anodic dissolution of iron in acidic media and the corre-
sponding cathodic reaction has been reported to proceed as follows
[27]:
2þ
Fe ! Fe þ 2e
2Hþ þ 2e ! 2Hads ! H2
As a result of these reactions, including the high solubility of the
corrosion products, the metal loses weight in the solution. Fig. 2a–d
shows the plots of weight loss versus time for mild steel in 0.5 M
H2SO4 without and with different concentrations of ALLOX at 303–
333 K, respectively. From the plots, it is evident that the weight loss
of mild steel in the different test solutions increases with time. The
non-uniformity and non-linearity of the curves of the weight loss
plot may be attributed to the presence of mill scale on the mild steel
surface. It may also suggest that the mild steel corrosion by H2SO4 is
a heterogeneous process involving several steps. Similar observa-
tion has been reported recently [27]. A further inspection of the plots
reveal that the weight loss of mild steel was reduced in the presence
of ALLOX compared to the free acid solution; an indication of inhib-
iting effect of acid corrosion of mild steel.
A comparison of corrosion rate of mild steel with temperature
(303–333 K) in the absence and presence of different concentra-
tions of ALLOX are dipicted in Fig. 3 and the calculated values pre-
sented in Table 1. From Table 1 and Fig. 3, it is clear that corrosion
rate in the presence of ALLOX increases with rise in temperature.
This may be due to the fact that corrosion of mild steel in acidic
environments is generally accompanied with hydrogen gas evolu-
tion and increase in temperature usually accelerates the evolution
of hydrogen which results in higher dissolution rate of the mild
steel [20]. Fig. 3 also reveals that the corrosion rate was reduced
in the presence of different concentrations of ALLOX with the low-
est value obtained at the highest concentration (10 lM) of ALLOX
used at all the temperatures studied.
The influence of temperature on percentage inhibition effi-
ciency was studied by conducting weight loss measurements at
303–333 K containing different concentrations of ALLOX (Table
1). Fig. 4 shows the variation of percentage inhibition efficiency
with temperature. It is clear from the figure that percentage inhi-
bition efficiency increases with concentration but decreases with
temperature. The increase in percentage inhibition efficiency of
ALLOX with concentration may be due to the adsorption of allox-
azine onto the mild steel surface though non-bonding electron
pairs present on nitrogen and oxygen atoms as well as p-electrons
[36]. The decrease in inhibition efficiency with increase in temper-
ature may be probably due to increased rate of desorption of
ALLOX from the mild steel surface at higher temperature [37].
The variation of the degree of surface coverage (h) with the log-
arithm of bulk concentration is presented in Fig. 5 for the corrosion
medium- ALLOX systems at 303–333 K. The pattern of the graphs
in Fig. 5 describes an S-shaped curve [38]. These indicate the for-
mation of a protective barrier film (adsorption) of inhibitor mole-
cules on mild steel surface. This implies that ALLOX act as
inhibitor by establishment of a thin film which acts as a barrier
to the transport of the metal ions from the metal to the solution.
267
3.2. Effect of temperature
Temperature has a great effect on the rate of metal electro-
chemical corrosion. In case of corrosion in a neutral solution (oxy-
gen depolarization) the increase in temperature has a favourable
effect on the overpotential of oxygen depolarization and the rate
of oxygen diffusion but it leads to a decrease of oxygen solubility.
In case of corrosion in acidic medium (hydrogen depolarization),
the corrosion rate increases exponentially with temperature
increase because the hydrogen evolution overpotential decreases
[39]. The relationship between the corrosion rate (q) of mild steel
in acidic media and temperature (T) is often expressed by the
Arrhenius equation [40,41]:
Ea
log q ¼ log A  ð5Þ
2:303RT
ð3Þ
ð4Þ where q is the corrosion rate Ea is the apparent activation energy, R
is the molar gas constant (8.314 J K1 mol1), T is the absolute tem-
perature, and A is the frequency factor. The plot of log q against 1/T
for mild steel corrosion in 0.5 M H2SO4 in the absence and presence
of different concentrations of ALLOX is presented in Fig. 6. All
parameters were given in Table 2.
The activation energy increased in the presence of ALLOX,
which indicated physical (electrostatic) adsorption [42]. Further-
more, the activation energy rose with increasing inhibitor concen-
tration, suggesting strong adsorption of inhibitor molecules at the
metal surface [43]. The increase in activation energy was due to the
corrosion reaction mechanism in which charge transfer was
blocked by the adsorption of ALLOX molecules on the mild steel
surface [44,45]. It also revealed that the whole process was con-
trolled by the surface reaction since the energy of the activation
corrosion process in both the absence and presence of ALLOX
was greater than 20 kJ mol1 [46].
Experimental corrosion rate values obtained from weight loss
measurements for mild in 0.5 M H2SO4 in the absence and pres-
ence of ALLOX was used to further gain insight on the change of en-
thalpy (DH ) and entropy (DS ) of activation for the formation of
the activation complex in the transition state using transition
equation [47]:
     
RT DS DH
q¼ exp exp ð6Þ
Nh R RT
where q is the corrosion rate, h is the Plank’s constant (6.626176 
1034 Js), N is the Avogadro’s number (6.02252  1023 mol1), R is
ρ
Fig. 6. Arrhenius plot for mild steel corrosion in 0.5 M H2SO4 in the absence and
presence of different concentrations of alloxazine (ALLOX).
268 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

Table 2 charge sharing or charge transfer from the inhibitor molecules to

Activation parameters of the dissolution of mild steel in 0.5 M H2SO4 in the absence the metal surface to form a coordinate type bond. In fact electron
and presence of different concentrations of ALLOX.
transfer is typically for transition metals having vacant low-energy
Conc. A (g cm2 h1) Ea (kJ mol1) DH* (kJ mol1) DS* (J mol1 K1) electron orbital. Chemisorption is typified by much stronger
Blank 1.18  104
40.99 180.07 207.97 adsorption energy than physical adsorption. Such a bond is there-
2 lM 1.78  104 42.29 184.86 220.80 fore more stable at higher temperatures.
4 lM 8.60  105 53.54 223.25 331.85 Basic information on the adsorption of inhibitor on metal sur-
6 lM 6.59  108 72.35 286.06 516.24
8 lM 1.77  1011 88.34 340.24 675.35
faces can be provided by adsorption isotherm. Attempts were
10 lM 5.62  1015 117.16 437.32 966.00 made to fit experimental data to various isotherms including
Frumkin, Langmuir, Temkin, Freundlich, Bockris-Swinkels and Flo-
ry-Huggins isotherms. All these isotherms are of the general form
[50]:
the universal gas constant and T is the absolute temperature. Fig. 7
shows the plot of log q/T versus 1/T for mild steel corrosion in f ðh; xÞ expð2ahÞ ¼ K ads C ð7Þ
0.5 M H2SO4 in the absence and presence of different concentrations
where f ðh; xÞ is the configurational factor which depends on the
of ALLOX. Straight lines were obtained with slope of (DH /2.303R)
physical mode and the assumptions underlying the derivation of
and an intercept of [log (R/Nh) + (DS /2.303R)] from which the values
the isotherm, h the degree of surface coverage, C the inhibitor con-
of DH and DS , respectively, were computed and listed also in Table
centration, x the size factor ratio, a the molecular interaction
2. Inspection of these data reveal that the activation parameters (DH
parameter, and Kads the equilibrium constant of the adsorption pro-
and DS ) of dissolution reaction of mild steel in 0.5 M H2SO4 in the
cess. In this study, correlation coefficient (R2) was used to deter-
presence of ALLOX are higher than in the absence of inhibitor. The po-
mine the best fit isotherm which was obtained from Temkin
sitive sign of the enthalpy of activation reflect the endothermic nat-
adsorption isotherm. According to this isotherm, h is related to
ure of steel dissolution process meaning that dissolution of steel is
the inhibitor concentration by the following equation [51]:
difficult [48]. The entropy of activation was also positive in the ab-
sence and presence of ALLOX implying that the rate-determining step expð2ahÞ ¼ K ads C ð8Þ
for the activated complex is dissociation step rather than association.
where the molecular interaction parameter a can have both positive
In other words, the adsorption process is accompanied by an increase
and negative values. Positive values of a indicate attraction forces
in entropy, which is the driving force for the adsorption of inhibitor
between the adsorbed molecules while negative values indicate
onto the mild steel surface [49].
repulsive forces between the adsorbed molecules [51]. Upon rear-
rangement of Eq. (8), the following equation is obtained:
3.3. Adsorption isotherm and thermodynamic consideration
h ¼ ½1=ð2aÞ lnðK ads CÞ ð9Þ
Generally speaking, corrosion inhibitors are found to protect If the parameter f is defined as:
steel corrosion in acid solutions by adsorbing themselves on steel
surface. Moreover, the adsorption process depends on the mole- f ¼ 2a ð10Þ
cule’s chemical composition, the temperature and the electro- where f is the heterogeneous factor of the metal surface describing
chemical potentials at the metal/solution interface. Adsorption is the molecular interactions in the adsorption layer and the heteroge-
a separation process involving two phases between which certain neity of the metal surface. Eq. (10) clearly shows that the sign be-
components can be described by two main types of interaction tween f and a is reverse, that is, if a < 0, then f > 0; if a > 0, then
[47]: (1) physisorption which involves electrostatic forces between f < 0. Accordingly, if f > 0, mutual repulsion of molecules occurs
ionic charges at the metal/solution interface. The heat of adsorp- and if f < 0 attraction takes place. If Eq. (10) is substituted into Eq.
tion is low and therefore this type of adsorption is stable only at (9), then the Temkin isotherm equation [52] has the following form:
relatively low temperatures and; (2) chemisorption which involves
h ¼ ð1=f Þ lnðK ads CÞ ð11Þ
where h is the degree of surface coverage, and could be calculated
by the following relationship [27]:
%I
h¼ ð12Þ
100
Eq. (11) can be transformed into:
h ¼ ð1=f Þ ln K ads þ ð1=f Þ ln C ð13Þ
Eq. (13) is a different form of the Temkin isotherm. The plot of h ver-
sus lnC gives a straight line graph with a slope of (1/f) and an inter-
cept of [(1/f)lnKads]. It is clear that f can be calculated from the slope,
with the calculated f, the value of Kads can be obtained from the
intercept. All the parameters are listed in Table 3. Fig. 8, is the
ρ

Table 3
Some parameters from Temkin isotherm model for mild steel in 0.5 M H2SO4.

Temperature (K) f Kads (M1) (R2) DGoads (kJ mol1)

303 6.09 1.68 0.987 10.32
313 7.04 1.17 0.991 10.14
323 9.61 0.94 0.941 10.25
Fig. 7. Transition state plot for mild steel corrosion in 0.5 M H2SO4 in the absence 333 10.86 0.42 0.900 9.88
and presence of different concentrations of alloxazine (ALLOX).
 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275 269

Fig. 9 shows the plot of lnKads versus 1/T which gives straight lines
with slope of (DHoads /R) and intercepts of (DSoads /R + ln 1/55.5).
Calculated value of DHoads and DSoads using the Van’t Hoff equation
are 13.60 kJ mol1 and 0.012 J mol1 K1, respectively.
The enthalpy and entropy for the adsorption of ALLOX on mild
steel were also deduced from the thermodynamic basic equation
[63]:

DGoads ¼ DHoads  T DSoads ð16Þ

θ

where DHoads and DSoads are the enthalpy and entropy changes of
adsorption process, respectively. A plot of DGoads versus T was linear
(Fig. 10) with the slope equal to DSoads and intercept of DHoads . The
enthalpy of adsorption DHoads , and the entropy of adsorption DSoads ,
obtained are 13.99 kJ mol1 and 0.018 J mol1 K1, respectively.
The negative sign of DHoads indicates that the adsorption of ALLOX
molecules is an exothermic process. In an exothermic process, phys-
isorption is distinguished from chemisorption by considering the
absolute value of DHoads . For physisorption process, the enthalpy of
adsorption is lower than 40 kJ mol1 while that for chemisorption
Fig. 8. The relationship between h and lnC at different temperatures. approaches 100 kJ mol1 [64]. In the present case, DHoads is lower
than 40 kJ mol1 clearly indicating that physical adsorption is in-
volved. Values of DHoads obtained by the two methods are in good
agreement.
relationship between h and lnC at different temperatures. These re-
The entropy of adsorption obtained from Eqs. (15) and (16) are
sults show that all the linear correlation coefficients (R2) are close to
negative because inhibitor molecule freely moving in the bulk solu-
1, which indicates that the adsorption of ALLOX onto steel surface
tion (inhibitor molecule were chaotic), were adsorbed in an orderly
obeys the Temkin adsorption isotherm. Furthermore, it can be de-
fashion onto the mild steel, resulting in a decrease in entropy [65].
duced that there is repulsion force in the adsorption layer due to
Moreover, from thermodynamic principles, since the adsorption
f > 0. Table 3 also indicates that the adsorption equilibrium constant
Kads values decrease with increasing temperature. Large values of
Kads mean better inhibition efficiency of the inhibitor, i.e., strong
electrical interaction between the double-layer existing at the
phase boundary and the adsorbing inhibitor molecules. Small val-
ues of Kads, however, reveal that such interactions between adsorb-
ing inhibitor molecules and the metal surface are weaker, indicating
that the inhibitor molecules are easily removable by the solvent
molecules from the metal surface [53]. These results confirm the
suggestion that ALLOX is physically adsorbed on the metal surface
and that the strength of the adsorption decreases with temperature.
Kads is related to the free energy of adsorption DGoads by the equa-
tion [54]:

DGoads
log K ads ¼  log C H2 O  ð14Þ
2:303RT
where C H2 O is the concentration of water expressed in mol/L (the
same as that of inhibitor concentration), R is the molar gas constant
(kJ mol1 K1) and T is the absolute temperature (K). Fig. 9. The relationship between lnKads and 1/T.
Calculated free energies DGoads values are given also in Table 3.
The negative values of DGoads indicate spontaneous adsorption of
ALLOX onto the mild steel surface [55] and strong interactions be-
tween inhibitor molecules and the metal surface [56]. Generally,
values of DGoads up to 20 kJ mol1 are consistent with physisorp-
tion, while those around 40 kJ mol1 or higher are associated
with chemisorption as a result of the sharing or transfer of elec-
trons from organic molecules to the metal surface to form a coor-
dinate bond [57–61]. The calculated values of DGoads are less than
20 kJ mol1, indicating that the adsorption mechanism of ALLOX
on mild steel in 0.5 M H2SO4 solution at the studied temperatures
Δ

is physisorption [43].
Thermodynamic parameters such as enthalpy of adsorption
DHoads and entropy of adsorption DSoads can be deduced from inte-
grated version of the Van’t Hoff equation expressed by [62]:

DHoads DSoads 1
ln K ads ¼  þ þ ln ð15Þ
RT R 55:5 Fig. 10. The relationship between DGoads and temperature.
270 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

Fig. 11. The plot of lnWt against t for mild steel corrosion in 0.5 M H2SO4 with and without ALLOX.

was an exothermic process, it must be accompanied by a decrease 0:693

in entropy [66].
3.4. Kinetics of mild steel corrosion in H2SO4 with and without
alloxazine
The kinetics of the mild steel corrosion in the absence and pres-
ence of different concentrations of ALLOX in 0.5 M H2SO4 was stud-
ied at 30 °C by fitting the corrosion data into different rate laws.
Correlation coefficients R2 were used to determine the best rate
law for the corrosion process. The rate laws considered were [67]:
Zero-order : W t ¼ kt
First-order : ln W t ¼ kt þ ln W o
t1=2 ¼ ð23Þ
k
The values of rate constant and half-life periods obtained are sum-
marized in Table 4. The value of the rate constant (k) was found to
be higher in the case of inhibited mild steel samples than uninhib-
ited samples whereas half-life (t1/2) was found to be lower in the
presence of inhibitor than in its absence. This implies that the cor-
rosion rate is higher in the absence of inhibitor than with inhibited
Table 4
ð17Þ The values of first-order rate constant, half-life and time constant for the dissolution
of mild steel in 0.5 M H2SO4 in the absence and presence of different concentrations of
ð18Þ ALLOX.

Conc. k (h1) t1/2 (h) s (h)

Second-order : 1=W t ¼ kt þ 1=W o ð19Þ
Blank 0.216 3.20 4.63
where Wo is the initial weight of mild steel, Wt is the weight loss of 2 lM 0.307 2.25 3.25
mild steel at time t and k is the rate constant. 4 lM 0.292 2.37 3.42
6 lM 0.388 1.78 2.57
By far best result was obtained for first-order kinetics. The plot 8 lM 0.286 2.42 3.49
of lnWt against t which was linear (Fig. 11) with good correlation 10 lM 1.043 0.66 0.95
coefficients (R2 > 0.9) confirms first-order kinetics for the corrosion
of mild steel in 0.5 M H2SO4 in the absence and presence of ALLOX.
The corrosion rate of mild steel in sulphuric acid medium is un-
der anodic control [68] which is:
rds
Fe þ OH ¡ FeOHads þ Hþ þ e ð20Þ
þ
FeOHads ! FeOH þ e ð21Þ

FeOHþ þ Hþ ¡ Fe2þ þ H2 O ð22Þ

where ‘rds’ stands for rate-determining step. a

Fig. 11 reflects the reaction order with respect to mild steel. This
b
result suggests that the presence of ALLOX does not influence the
anodic reaction order. The linearity of the curves in the absence
and presence of ALLOX implies that its presence does not change
the kinetics of the corrosion reaction though the rate might be con-
siderably reduced. Similar report has been documented elsewhere
[69].
The half-life (t1/2) value was calculated [70] using the following Fig. 12. UV–Visible spectra of the solution containing 0.5 M H2SO4 (10 lM) ALLOX
relationship: (a) before and (b) after 3 days of mild steel immersion.
 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275 271

mild steel samples. Similar results were reported on the kinetics of
some organic compounds [71].
Another indication of the rate of a first-order reaction is the
time constant, s, [71]. The time required for the concentration of
the reactant to fall to 1/e of its initial value. The calculated values
of the time constants are also presented in Table 4. The results
show that the time constants were lower in the presence of ALLOX
than in its absence. This confirms that the presence of the inhibitor
decreases the dissolution of mild steel.
3.5. UV–Visible spectroscopic investigation
The adsorption of monochromatic light according to Abboud
et al. [72], is a suitable method for identification of complex ions.
The adsorption of light is proportional to the concentration of the
adsorbing species. For routine analysis, a simple conventional tech-
nique based on UV–Visible absorption is the most sensitive direct
spectrophotometric detection. Change in position of the absor-
bance maximum and change in the value of absorbance indicate
the formation of a complex between two species in solution [73].
In order to confirm the possibility of the formation of ALLOX-Fe
complex, UV–Visible absorption spectra obtained from 0.5 M
H2SO4 solution containing 10 lM ALLOX before and after 3 days
of mild steel immersions are shown in Fig. 12.
The absorption spectrum of the solution containing 10 lM
ALLOX before the steel immersion (Fig. 12) shows an adsorption
band in the range of 330–400 nm. It has been reported that allox-
azine spectra in the near-UV have maxima at about 340–400 nm
[18]. The absorption band at this longer wavelength is as a result
of the presence of aromatic system in ALLOX which is highly con-
jugated. Furthermore, the presence of lone pair of electrons on the
alloxazine nitrogens atoms and/or carbonyl group give rise to the
spectra around 330 nm due to n-p* transition. After 3 days of steel
immersion (Fig. 12), it is clearly seen that the band shifted to a
longer wavelength (390–470 nm) and there is a decrease in absor-
bance. It is clear that there was no significant difference in the
shape of the spectra before and after the immersion of ALLOX
showing a possibility of weak interaction between ALLOX and mild
steel (physisorption). Alloxazines are multifunctional with numer-
ous electron donor sites and has been reported as a potential ligand

Fig. 13. Optimized structure of alloxazine (ALLOX) (ball and stick model).

Fig. 14. The highest occupied molecular orbital (HOMO) density of alloxazine (ALLOX) using DFT at the B3LYP/6-31G (d,p) basis set level.
272 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

for metal centres, which in the absence of additional coordination
sites bind predominantly through N(4) and O(2) to form five-mem-
bered, redox active a-iminoketo chelate rings [74]. These experi-
mental findings give strong evidence for the possibility of the
formation of a complex between Fe2+ cation and ALLOX in H2SO4.
3.6. Quantum chemical studies
The density functional theory (DFT) is one of the most impor-
tant theoretical models used in explaining the science of solids
and chemistry. A number of chemical concepts have been corre-
lated within the framework of DFT [75]. The most fundamental
parameter in DFT is the electron density q(r) upon which all the
chemical quantities are expressed [76]. The structural parameters
calculated through the q(r) concept, compare well with the param-
eters calculated by the W concept [77]. Since the theory is simpler
than quantum mechanics, the interest has grown in understanding
the structure, properties, reactivity, and dynamics of atoms, mole-
cules and clusters using DFT. In the field of reaction chemistry, DFT
exceeds the limit of wave mechanics [78], and it is emerging as a
unique approach for the study of reaction mechanism [79].
Recently, the density functional theory (DFT) has been used to
analyze the characteristics of the inhibitor/surface mechanism
and to describe the structural nature of the inhibitor on the corro-
sion process [80–82]. Furthermore, DFT is considered a very useful
technique to probe the inhibitor/surface interaction as well as to
analyze the experimental data. Thus in the present investigation,
quantum chemical calculation using DFT was employed to explain
the experimental results obtained in this study and to further give
insight into the inhibition action of ALLOX on the mild steel
surface.
For the purpose of determining the active sites of the inhibitor
molecule, three influence factors: natural atomic charge, distribu-
tion of frontier orbital, and Fukui indices are considered. According
to classical chemical theory, all chemical interactions are by either
electrostatic or orbital. Electrical charges in the molecule were
obviously the driving force of electrostatic interactions it has been
proven that local electron densities or charges are important in
many chemical reactions and physico-chemical properties of com-
pound [83]. Figs. 13–16 show the optimized geometry, the HOMO
density distribution, the LUMO density distribution and the Mul-
liken charge population analysis plots for ALLOX molecule ob-
tained with DFT at B3LYP/6-31G (d,p) level of theory.
The reactive ability of the inhibitor is considered to be closely
related to their frontier molecular orbitals, the HOMO and LUMO.
Higher HOMO energy (EHOMO) of the molecule means a higher

Fig. 15. The lowest unoccupied molecular orbital (LUMO) density of alloxazine (ALLOX) using DFT at the B3LYP/6-31G (d,p) basis set level.

Fig. 16. Mulliken charges population analysis of alloxazine (ALLOX) using DFT at the B3LYP/6-31G (d,p) basis set level.
 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275
electron-donating ability to appropriate acceptor molecules with
low-energy empty molecular orbital and thus explains the adsorp-
tion on metallic surfaces by way of delocalized pairs of p-electrons.
ELUMO, the energy of the lowest unoccupied molecular orbital signi-
fies the electron receiving tendency of a molecule. Accordingly, the
difference between ELUMO and EHOMO energy levels (DE = ELUMO 
EHOMO) and the dipole moment (l) were also determined. The
global hardness g is approximated as DE/2, and can be defined un-
der the principle of chemical hardness and softness (HSAB) [84].
These parameters also provide information about the reactive
behavior of molecules and are presented in Table 5. These theoret-
ical parameters were calculated in the gas phase, aqueous phase as
well as in the protonated form of ALLOX. The calculated parame-
ters in gas phase as well as in the presence of a solvent did not
exhibit important differences.
From Figs. 14 and 15, it could be seen that ALLOX have similar
HOMO and LUMO distributions, which were all located on the en-
tire alloxazine moiety. This is due to the presence of nitrogen and
oxygen atoms together with several p-electrons on the entire mol-
ecule. Thus, unoccupied d-orbitals of Fe atom can accept electrons
from inhibitor molecule to form coordinate bond. Also the inhibitor
molecule can accept electrons from Fe atom with its anti-bonding
orbitals to form back-donating bond. Fig. 16 shows the Mulliken
atomic charges calculated for ALLOX. It has been reported that
the more negative the atomic charges of the adsorbed centre, the
more easily the atom donates its electron to the unoccupied orbital
of the metal [84]. It is clear from Fig. 16, that nitrogen and oxygen
as well as some carbons atoms carries negative charge centers
which could offer electrons to the mild steel surface to form a coor-
dinate bond. Among the nitrogen atoms, the highest negative
charge is domiciled in N4 while among the oxygen atoms the high-
est negative charge is found in O2. This shows that the two atoms
are the probable reactive sites for the adsorption of iron.
Higher values of EHOMO are likely to indicate a tendency of the
molecule to donate electrons to appropriate acceptor molecules
with low energy or empty electron orbital. It is evident from Table
5 that alloxazine has the highest EHOMO in the gas and aqueous
phase and a lower EHOMO in the protonated form. This means that
the electron-donating ability of ALLOX is weaker in the protonated
form. This confirms the experimental results that interaction be-
tween ALLOX and mild steel is electrostatic in nature (physisorp-
tion). The energy of the LUMO is directly related to the electron
affinity and characterizes the susceptibility of the molecule to-
wards attack by neuclophiles. The lower the values of ELUMO are,
the stronger the electron accepting abilities of molecules. It is clear
from Table 4 that the protonated form of ALLOX exhibits the lowest
EHOMO, making the protonated form the most likely form for the
interaction of mild steel with alloxazine molecule. Low values of
the energy gap (DE) will provide good inhibition efficiencies, be-
cause the excitation energy to remove an electron from the last
occupied orbital will be low [85]. A molecule with a low energy
gap is more polarizable and is generally associated with a high
chemical reactivity, low kinetic stability and is termed soft mole-
cule [86]. According to Wang et al. [87], adsorption of inhibitor
onto a metallic surface occurs at the part of the molecule which
has the greatest softness and lowest hardness. The result from
Table 5
Some molecular properties of alloxazine calculated using DFT at the B3LYP/6-31G
(d,p) basis set.
Inhibitor EHOMO ELUMO DE l g
(eV) (eV) (eV) (D)
ALLOX (gas phase) 6.78 2.74 4.04 4.24 2.02
ALLOX (aqueous phase) 6.78 2.74 4.04 4.24 2.02
ALLOX (protonated at N2) 11.33 7.45 3.88 7.98 1.94
273
Table 4 shows that ALLOX in the protonated form has the lowest
energy gap and lowest hardness; this agrees with the experimental
results that ALLOX could have better inhibitive performance on
mild steel surface in the protonated form i.e. through electrostatic
interaction between the cation form of ALLOX and the vacant
d-orbital of mild steel (physisorption). This also agrees well with
the value of DGoads and DHoads obtained experimentally. The dipole
moment is another important electronic parameter that results
from non-uniform distribution of charges on the various atoms in
a molecule. It is mainly used to study the intermolecular interac-
tions involving the Van der Waals type dipole–dipole forces etc.,
because the larger the dipole moment the stronger will be the
intermolecular attraction [86]. The dipole moment of ALLOX is
highest in the protonated form (7.98 Debye (26.614  1030 Cm)),
which is higher than that of H2O (l = 6.23  1030 Cm). The high
value of dipole moment probably increases the adsorption be-
tween chemical compound and metal surface [88]. Accordingly,
the adsorption of ALLOX molecules can be regarded as a quasi-sub-
stitution process between the ALLOX compound and water mole-
cules at the electrode surface.
The local reactivity of the ALLOX was analyzed through an eval-
uation of the Fukui indices [89]. These are measurements of the
chemical reactivity, as well as an indicative of the reactive regions
and the nucleophilic and electrophilic behavior of the molecule.
The regions of a molecule where the Fukui function is large are
chemically softer than the regions where the Fukui function is
small, and by invoking the HSAB principle in a local sense, one
may establish the behavior of the different sites with respect to
hard or soft reagents. The Fukui function f(r) is defined as the first
derivative of the electronic density q(r) with respect to the number
of electrons N at a constant external potential v(r). Thus, using a
scheme of finite difference approximations from Mulliken popula-
tion analysis of atoms in ALLOX and depending on the direction of
electron transfer we have [89]:
fkþ ¼ qk ðN þ 1Þ  qk ðNÞ ðfor nucleophilic attackÞ ð24Þ
fk ¼ qk ðNÞ  qk ðN  1Þ ðfor electrophilic attackÞ ð25Þ
q ðN þ 1Þ  qk ðN  1Þ
fko ¼ k ðfor radical attackÞ ð26Þ
2
where qk is the gross charge of atom k in the molecule i.e. the elec-
tron density at a point r in space around the molecule. The N corre-
sponds to the number of electrons in the molecule. N + 1
corresponds to an anion, with an electron added to the LUMO of
the neutral molecule; N  1 corresponds to the cation with an elec-
tron removed from the HOMO of the neutral molecule. All calcula-
tions were done at the ground-state geometry. These functions can
be condensed to the nuclei by using an atomic charge partitioning
scheme, such as Mulliken population analysis in Eqs. (24)–(26).
The calculated Fukui indices for the charged species (N + 1 and
N  1) as well as the neutral specie (N) are presented in Table 6. For
simplicity, only the charges and Fukui functions over the Nitrogen
(N), and oxygen (O) are presented. For a finite system such as an
inhibitor molecule, when the molecule is accepting electrons one
has fkþ , the index for nucleophilic attack; when the molecule is
donating electrons, one has fk , the index for electrophilic attack.
It is possible to observe from Table 6 that the nitrogen atoms in
the alloxazine ring (N2, N3 and N4) are the most susceptible sites
for electrophilic attacks. These sites present the highest values of
fk which are 0.003 for N1, 0.0028 for N2, and 0.0039 for N4,
respectively. On the other hand N4, N3 are the most susceptible
x sites for nucleophilic attacks. These sites have the highest values
of fkþ which are 0.01 for N4 and 0.003 for N3, respectively. Further-
5.61 more, of the two oxygen atoms in alloxazine, O2 has the highest
5.61
value of fkþ (Table 6). This result also confirms the work of Kaim
22.71
et al. [74] that alloxazine bind predominantly through N4 and O2
274 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275

Table 6
Calculated Mulliken atomic charges, Fukui functions and philicity indices for heteroatoms of alloxazine using DFT at the B3LYP/6-31G (d,p) basis set.

Atom qN qNþ1 qN1 fkþ fk fko xþk xk

N1 0.568 0.615 0.483 0.047 0.086 0.067 1.067 1.953
N2 0.519 0.642 0.523 0.123 0.003 0.060 2.793 0.068
N3 0.611 0.605 0.614 0.003 0.0028 0.005 0.068 0.006
N4 0.639 0.629 0.600 0.010 0.004 0.015 0.227 0.088
O1 0.455 0.553 0.387 0.098 0.068 0.083 2.225 1.544
O2 0.483 0.565 0.391 0.081 0.092 0.086 1.839 2.089

with a metal ion.Recently, Parr et al. [90], have introduced an elec-

trophilicity index (x) defined as:

v2
x¼ ð27Þ
2g
This was proposed as a measure of the electrophilic power of a mol-
ecule. The higher the value of x, the higher the capacity of the mol-
ecule to accept electrons.
In Eq. (27), v is electronegativity and g is global hardness. For v Fig. 17. Proposed structure of the complex compound formed between alloxazine
and Fe2+.
and g, their operational and approximate definitions are [87]:
IþA
v¼ ð28Þ
2 species (Eq. (34)) which may be adsorbed on the cathodic sites of
IA the mild steel and reduce the evolution of hydrogen:
g¼ ð29Þ
2
ALLOX þ 2Hþ $ ½ALLOXH2þ ð34Þ
According to Koopman’s theorem [91], the energies of the HOMO
and the LUMO orbitals of the inhibitor molecule are related to the The protonated ALLOX, however, could be attached to the mild steel
ionization potential, I, and the electron affinity, A, respectively, by surface by means of electrostatic interaction between SO24 and pro-

the following relation [92]:
I ¼ EHOMO
A ¼ ELUMO
In order to provide a unified treatment of chemical reactivity
and selectivity a new concept of philicity has been introduced re-
cently by Chattaraj et al. [93]. This local philicity index is given as:
xa ðrÞ ¼ xf a ðrÞ
or its condensed-to-atom variant for the atomic site k in a molecule
is defined as:
xak ¼ xfka
where a = +, , o refer to nucleophilic, electrophilic and radical at-
tacks, respectively. The xak is capable of providing other local and
global reactivity descriptors.
The electrophilic or nucleophilic power is distributed over all
atomic sites in a molecule keeping the overall philicity conserved.
The atomic site with the largest xþk will be the most favourable site
for nucleophilic attack, the highest xk for the electrophilic attack
and the highest xok for the radical attack [93]. From Table 5, it is
clear that x is highest for the protonated form of ALLOX inferring
that in this form, ALLOX has the highest capacity to accept elec-
trons from the vacant d-orbital of iron. On the other hand, xþ k is
highest in the N4 and N3 centers (Table 6) signifying that the
nucleophilic attack will take place on these atoms. For all the
atoms of ALLOX, x k is highest on N2 and N3 indicating that these
sites would be most favourable for electrophilic attack say
(protonation).
3.7. Mechanism of inhibition action of alloxazine on mild steel
From the experimental and theoretical results obtained, we
note that a plausible mechanism of corrosion inhibition of mild
steel in 0.5 M H2SO4 by alloxazine may be deduced on the basis
of adsorption. In acidic solutions the inhibitor can exist as cationic
tonated ALLOX since the steel surface has positive charges in the
acid medium [94]. This could futher be explained based on the
ð30Þ assumption that in the presence of SO2 4 , the negatively charged
ð31Þ SO2
4 would attach to positively charged surface. When ALLOX ad-
sorbs on the steel surface, electrostatic interaction takes place by
partial transference of electrons from the polar atoms (N and O
atoms and the delocalized p-electrons around the heterocyclic
rings) of ALLOX to the metal surface. In addition to electrostatic
ð32Þ interaction (physisorption) of ALLOX molecules on the steel surface,
molecular adsorption may also play a role in the adsorption process.
A close examination of the chemical structure of alloxazine, re-
veals that ALLOX molecules have structure characterized by the
presence of chelation centers mainly located on nitrogens and oxy-
ð33Þ
gen. From theoretical and experimental results obtained, N4 and
O2 are the likely sites of complexation of ALLOX with the Fe2+
(Fig. 17) which will result in the formation of a five-membered, re-
dox active a-iminoketo chelate rings [74]. The UV–Visible absorp-
tion spectra of the solution containing the inhibitor after the
immersion of the mild steel speciment indicated the formation of
a complex with the steel surface allowing the formation of adhe-
sive film. Such an adhesive film covered the metal surface isolating
the metal surface from the corrosive media.
4. Conclusions
The following conclusions may be drawn from the study:
(1) Alloxazine (ALLOX) acts as an inhibitor for the corrosion of
mild steel in 0.5 M H2SO4. Inhibition efficiency values
increase with the inhibitor concentration but decrease
with rise in temperature suggesting physical adsorption
mechanism.
(2) The adsorption of ALLOX on steel surface was found to
accord with Temkin adsorption isotherm model. The adsorp-
tion process is spontaneous, exothermic and accompanied
with a decrease in entropy of the system from thermody-
namic point of view.
 N.O. Obi-Egbedi, I.B. Obot / Corrosion Science 53 (2011) 263–275 275

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